Vinyl chloride polymers plasticized with adducts of alkyl fumarates and mesityl oxide



United States VINYL CHLORIDE POLYMERS PLASTICIZED WITH ADDUCTS OF ALKYL FUMARATES LAND MESITYL OXIDE Joachim Dazzi, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware 4 Claims. (Cl. 260-313) This invention relates to keto-esters and more particularly provides new and valuable ketonic dicarboxylates, a process of producing the same and vinyl chloride polymers plasticized with said new compounds.

An object of the invention is the provision of new and useful unsaturated keto-esters. Another object of the invention is the preparation of useful addition products of mesityl oxide and certain esters of fumaric acid. A further object of the invention is to provide for the synthetic resins and plastics, rubber and textile industries, a new class of stable, viscous compounds of high carboxylate content.

These and other objects hereinafter disclosed are provided by the following invention wherein keto-esters are prepared by the addition reaction of mesityl oxide and an alkyl fumarate. The reaction is one of simple addition in which one mole of the mesityl oxide adds to one mole of the fumarate substantially according to the scheme:

R-l-YOOC.CH RCHCOOY I CIELCOOY CHZCOOY' in which R denotes mesityl oxide and Y and Y are alkyl radicals of from 1 to 8 carbon atoms.

Although it is believed that the 1,2-dicarboxyethyl radical is attached at a carbon atom which is adjacent to that which bears the olefinic double bond of the mesityl oxide, the exact position at which the dicarboxyethyl radical is present is not exactly known. However, it is known that a ketonic carbonyl group is present in the addition prodnet and that the addition takes place at a saturated carbon atom and not at the olefinic double bond of the mesityl oxide. The oletinic double bond remains in the adduct.

Alkyl fumarates which may be employed in preparing the present adducts are the simple or mixed alkyl fumarates such as methyl, ethyl, n-propyl, isopropyl, butyl, isoamyl, n-hexyl, n-octyl, Z-ethylhexyl fumarate, ethyl methyl fumarate, ethyl n-propyl fumarate, isopropyl n-octyl fumarate, etc.

Reaction of the mesityl oxide with the alkyl fumarates to form the 1:1 addition products takes place readily by heating the mesityl oxide with the fumarate in the presence or absence of an inert diluent or solvent at ordinary or super-atmospheric pressure. When operating at atmospheric pressure, temperatures of from, say ZOO-300 C. and preferably of from 2l0-280 C. are used, Usually the lower alkyl fumarates are more reactive than the higher alkyl fumarates. In view of the effect of the reaction conditions and nature of the furnarate upon the extent to which the fumarate enters into the reaction, it is recommended that for each initial run optimum operating conditions be experimentally determined.

Since the alkyl fumarates employed in the present reaction are generally miscible with mesityl oxide under the reaction conditions used, no extraneous solvent or atent O F Patented May 16, 1961 ICE diluent need generally be employed. For successful reaction a diluent may or may not be present. Reaction is advantageously eflected in an inert atmosphere, e.g., in nitrogen or in carbon dioxide; and for good yields of product within comparatively short reaction times operation in a closed vessel, i.e., at pressures above atmospheric, is recommended.

In practice, the mesityl oxide and the fumarate are mixed in a reaction vessel and the mixture is heated, say, at the refluxing temperature thereof, for a time of, say, a few hours to a day. Completion of the reaction may be noted by cessation in change of refractive index upon continued heating.

The present 1:1 mesityl oxide-alkyl fumarate adducts are stable, viscous liquids, They are valuable for a variety of commercial and technical uses, e.g., as lubricant adjuvants, as intermediates for the preparation of resins, as moisture-proofing agents, etc. They are particularly valuable as plasticizers for polyvinyl chloride and copolymers of at least 70% by weight of vinyl chloride and up to 30% by weight of an unsaturated monomer copolymerizable therewith, for example, vinyl acetate, vinylidene chloride, etc. The present olefinic keto-esters impart great flexibility to vinyl chloride polymers at low temperatures; they are compatible with such polymers and show no exudation of plasticizer even at plasticizer content of up to 50%. Although the quantity of plasticizer will depend upon the particular polymer to be plasticized and upon its molecular weight it is generally found that compositions having from 5% to 50% by weight of the present adducts will, in most cases, "be satisfactory for general utility. The good flexibility of the plasticized compositions increases with increasing plasticizer concentration.

The present invention is further illustrated but not limited by the following examples:

Example 1 A mixture consisting of g. (1.5 moles) of mesityl oxide, 684 g. (3 moles) of butyl furnarate and l g. of di-tert-butylcatechol as polymerization inhibitor was heated in a closed vessel at 220 C, for 12 hours. During the heating period the refractive index of the mixture rose from 11 1.4392 to 21 1.4478. Distillation of the resulting reaction mixture to remove material boiling below 220' C./l mm. gave as residue 104.5 g. of the 1:1 mesityl oxide-dibutyl fumarate adduct, n 1.4752, analyzing as follows:

.Fonnd Caled. for

Percent C 67. 13 66. 2 Percent H 8. 76 9. 24

Infra-red spectrographic analysis of said adduct showed the presence therein of a conjugated ketonic carbonyl group at 5.9 the presence of an olefinic double bond at 6.1,u; and the presence of ester carbonyl groups at 5.8;1. and 8.411..

Example 2 appease? ""of'3'.9%.' When subjected'to heat at a temperature of "S25*'F.'for a periodof 30minutes-theclarity and color of the molded product wassubstantially unchanged. Tests of the water resistance properties .of the plasticized ma- The plasticized polyvinyl halide compositions of the present invention -have good thermal stability; however, for many purposes it may be advantageous to use known stabilizers in the plasticized compositions. Inasmuch tterial byimmersing'themolded'specimen for-24 ho rs in as the present adducts are substantially unreactive with water gave a water ab orp i n 'v l e'of. .4 n a the commercially available-heat and light stabilizers I solids loss valueof 0.0%. which are commonly employed. withpolyyinyl, chloride Kerosenerresistance Of the ,moldedtest, specimenwas or. copolymersthereof thehbresence, ,of suchif jjtrials determined as follows: in the plasticized products does not impair theyaluable A 2" diameter'40 mil disc'wass pe e @15 properties of the adducts. The present adducts are of g oven for a- 3-h r conditioning p o eliminate water, 7, general utility in softening vinyl chloride-polymers. They t ihen and Weighed? The CGIlditiOnod Sample was may be used as the only plasticizer components in a thenimmersedin .400, ml. o'f kerosene for a period of compounded vinyl chloride polymer or they may be 24 hours, at 27C. The sample was then remov d f o used in conjunction with othehplasticizers. ...the kerosene, blotted dryiand suspended in a force-draft Thi application is divi io f my. pending ,ap 1i 30 C- v n for 4 hOufSI 'The pl w then lCOOlEd tion, Serial No. 572,636; filedMarch-20,.1956, :.which and weighed. The. percent. loss. in weight thus .deterissued as Patent No. 2,883,419, dated April Zl, 1939. .Qrnined, si.e.,..the.keroseneextractionflalfle, was found What I claim is: hwto -beronly 0.5%. 1. A resinous composition comprising a resinous i- Addu t f gther alkyL f maratesand mesityl oxide polymer selected from the class consisting of homolikewise possess :very. .goodlplasticizing. properties f I polymers of vinyl ,chlorideand copolymers"oftvihylchlm @yinyl chloride polymers. Thus, by employing 0 pa ride with mono-ethylenic unsaturated monomerslsaid ',..-by .:weight 0f.tthe,..addllct 0f; mesityl. oxide and ethyl copolymers containing at l east 7o%. byjwe ight xhfumarate, .bis(2-ethylhexyl) -fumarate, or isopropyl chloride combinedflthereimand said resinousfpolymer I.methyli .fumarate with 60 partsby-weight. of polyvinyl being plasticized with an adductfin. whichone mole of chloride or with 60 parts by weig t. o a vinyl chloridemesityloxide is :chemically c ornbined withione mlole of vinyl acetate copolymer-known to the trade. as Vinylite a dialkyl fumarate having from 1 to 8 car horiflalto sin :.:-there may be obtained clear, colorless compositionsiof each alkyl radical, said adduct havingbeen prepared vvery good flexibility'andstability. by heatingthe mesityl oxide with .th e furnara'te. A

' -While the abovefexarnples show only compositions 2. A resinous compositioncomprising -polyvinyl chlo ,-.--.-in which the ratio of iplasticizento polymer ,content is ride plasticized with an adduct in vvhich one mole of 40:60, this ratio-being employed in order to, get commesityl oxide'is chemically combined withonejmole of .parable.efliciencies, the content of:ester tolpolyvinyl chloa dialkyl fumarate having from 1 to 8,carbon atoms ride may be widely-yaried, depending upon the properties in each alkyl radica l,. sa adducthaving been prepared f -desired in the final product: .For many purposes a by heating the mesityl oxide with thefumarate. i zplasticizer content of, say, fromonly 10 percent to 20 3. A resinous.compositioncomprising a copolymer. of percent is preferred. The present adducts are compatible at least 70% by weight of .vinyl. chloride and up to 30% mwith .polyvinyl chloride--overwide-ranges of concentraby weight of a monoethyleni'cally unsaturated comonorner, tions, up to 50 percentof: adduct,;based; on the total 40 said copolymer being plasticized with anadduct in which weight of the plasticized composition yielding desirable one mole of mesityl. oxide is chemically combined with products. one mole of a dialkyl fumarate having from 1 to 8 car- Although the invention has been describedgparticularly bon atoms in each alkyl radical, said adduct having been with reference to the use of the present adducts as plasprepared by heating mesityl oxide with the fumarate. "-"ticizers for polyvinyl chloride,-these'adductsare ad- 4. A resinous composition comprising polyvinylchlo- --'-vantageously employed also as plasticizersrforcopolymers ride plasticized with, an adduct in;which one moleof 'of vinyl chloride, for example, thezcopolymers of vinyl mesityl oxide is chemically combined with one mole chloride with vinyl acetate,-uvinylidene chloride, etc. of' dibutyl fumarate, said adducthaving been prepared Preferably, suchcopolymers: have ahigh .vinyl chloride by. heating mesityl oxide with dibutyl fumarate. 1 content, Le, a vinyl chloride content of at least 70 percent by weight of vinyl chloride andiup to-30 percent No e e n es ited.

by weight of the copolymerizable monomer. 

1. A RESINOUS COMPOSITION COMPRISING A RESINOUS POLYMER SELECTED FROM THE CLASS CONSISTING OF HOMOPOLYMERS OF VINYL CHLORIDE AND COPOLYMERS OF VINYL CHLORIDE WITH MONO-ETHYLENIC UNSATURATED MONOMERS, SAID COPOLYMERS CONTAINING AT LEAST 70% BY WEIGHT OF VINYL CHLORIDE COMBINED THEREIN, AND SAID RESINOUS POLYMER BEING PLASTICIZED WITH AN ADDUCT IN WHICH ONE MOLE OF MESITYL OXIDE IS CHEMICALLY COMBINED WITH ONE MOLE OF A DIALKYL FUMARATE HAVING FROM 1 TO 8 CARBON ATOMS IN EACH ALKYL RADICAL, SAID ADDUCT HAVING BEEN PREPARED BY HEATING THE MESITYL OXIDE WITH THE FUMARATE. 